Partially fluorinated naphthyl-based borates

ABSTRACT

Non-coordinating anions or anion precursors are disclosed. These non-coordinating anions serve as the activator for olefin polymerization catalyst systems. As such, they abstract an alkyl leaving group from a metallocene catalyst precursor leaving an activated catalyst charge balanced by a non-coordinating anion. These anions are formed by 3 or 4 partially fluorinated naphthyl ligands coordinated around boron (or other Group-13 element) creating corresponding tris-borane or tetrakis-borate complexes.

TECHNICAL FIELD

This invention relates to the use of noncoordinating anions suitable forstabilizing cationic olefin polymerization catalyst compounds.

BACKGROUND

Noncoordinating anions, in which boron connects to perfluorinated phenylligands that increase the anion's lability and stability with respect toun-wanted reactions with the metal cation complexes, are known. (U.S.Pat. No. 5,198,401). Examples of these includetetrakis(pentafluorophenyl)borate, [B(PfP)₄]⁻ or [B(C₆F₅)₄]⁻. Suitablearyl radicals other than phenyl radicals, e.g. naphthyl and anthracenyl,are described. U.S. Pat. No. 5,296,433 describes borane complexescomprising tris(pentafluorophenyl)borane and specific complexingcompounds. These complexes polymerize higher molecular weight polymerswhen used with metallocene catalysts apparently due to their increasedmonomer or monomer solution solubility. WO 97/29845 describes preparingperfluorobiphenyl borane and using this Lewis acid to prepare andstabilize active olefin-polymerization catalysts. Apparently, thesecocatalysts are less coordinating than tris(perfluorophenyl)boron,B(C₆F₅)₃ and yield higher catalytic activities. That document describescocatalysts with the formula BRR″ where B is boron, and R′ and R″represent one or more fluorinated biphenyl's or other polycyclic groups,such as naphthyl, anthryl or fluorenyl.

Olefin solution-polymerization processes are generally conducted inaliphatic solvents to maintain reaction temperature and solvate thepolymer product. But aryl-group-containing activators dissolve poorly insuch solvents. Typically, activators are introduced in toluene or otheraryl solvents. Thus, toluene contaminates aliphatic-solvent-basedprocesses. It must be removed because it tends to harm processefficiency. Moreover, aryl-based solvents may be unhealthful inlarge-scale polymerization and in the resulting polymer. Alternatively,slurries can transport the activators, but that complicates their useand increases plant design costs and operation costs. Low solubilityproblems are exacerbated when processes involve a low temperature stage,e.g. adiabatic processes run in colder climates. Additionally,separating the solvent or counteracting its build up in the recyclesystem presents other problems that counter industrial goals. One goalof those is to maintain high polymer molecular weights while operatingat high reaction temperatures and high polymer production rates.Therefore, industry desires higher aliphatic solubility for cocatalystactivators.

U.S. Pat. No. 5,502,017 discloses metallocene olefin-polymerizationcatalysts that contain a weakly coordinating anion based on boronsubstituted with halogenated aryl or silylallyl substituents, such astert-butyl-dimethyl-silyl. Apparently, this substitution increases themetallocene salt's solubility and thermal stability. Examples 3-5describes the synthesis of and polymerization with the cocatalyst:triphenylcarbenium tetrakis(4-dimethyl-t-butylsilyl-2,3,5,6-tetrafluorophenyl)borate.

Thus, a need exists for cocatalyst compounds that improve solutionpolymerization economics and that provide alternative activators forolefin-polymerization catalyst systems.

SUMMARY

Invention bulky noncoordinating anions are surprisingly stable underpolymerization conditions. They allow high-molecular-weight polymerpreparation with catalyst efficiencies sometimes exceeding prior artteachings. Thus, the invention is directed to a polymerization processwhere one or more ethylenically unsaturated monomers are contacted witha catalyst containing at least one organometallic transition metalcompound. Before contacting with the monomers, a non-coordinatingGroup-13 complex activates the transition metal to a cationic state.This Group-13 complex has a Group-13 element tetrahedrally coordinatedby partially halogenated polycyclic fused rings. Other invention aspectsinclude non-coordinating activators containing partially halogenatedpolycyclic fused-rings and catalyst systems that contain suchactivators. Catalyst systems typically have at least one catalystprecursor and at least one activator. Another aspect of the inventionincludes a method of making non-coordinating Group-13 elementtetrahedrally coordinated by partially halogenated polycyclic fusedrings.

DETAILED DESCRIPTION

Invention activating cocatalyst precursors (activators) compriseGroup-13 complexes having halogenated aromatic ligands. These ligandscontain polycyclic phenyl ring assemblies in which two or more rings arefused to form fused-ring systems. The Group-13 central core connects tothese ligands such that the complex has an essentially tetrahedralarrangement around the Group-13 core when anionic, i.e. fourcoordinating ligands, or an essentially planar arrangement around theGroup-13 core when neutral, i.e. three coordinating ligands. Someembodiments select naphthyl as the polycyclic moiety.

A feature of these ring assemblies is that they are partiallyhalogenated or fluorinated. In some embodiments, partial means at leastone ring assembly is halogen or fluorine substituted, while at least onering assembly is not. An exemplary noncoordinating anion has ligands(fused-ring assemblies) as shown below.

This ligand forms the anion shown below.

tetrakis(5,6,7,8-tetranaphth-2-yl)borate

Alternatively, the corresponding naphthyl borane may be formed.

tris(5,6,7,8-tetrafluoronaphth-2-yl)borane

In other embodiments, partially fluorinated or halogenated examplesinclude examples with less than complete fluorination or halogenation onat least one ring and no fluorination or halogenation on at least onering.

Halogenation or fluorination encompasses fused-ring hydrogen replacementby halogen or fluorine, replacement by a perfluorinated orperhalogenated alkyl, or replacement by a substantially fluorinated orsubstantially halogenated alkyl. Substantially fluorinated orhalogenated means being less than perfluorinated or perhalogenated butfluorinated or halogenated enough to provide a commercially usefulimprovement over corresponding unfluorinated or unhalogenated species.Put another way, substantially fluorinated means that enough hydrogenatoms have been fluorine-or halogen-replaced so that any remaininghydrogen are not acidic enough to deactivate catalytic sites. While somesites may be deactivated by reaction with hydrogen atoms, not enoughsites will be deactivated to harm the catalyst systems' commercialutility.

Transition metal olefin polymerization catalysts for ethylenicallyunsaturated olefins are typically stable, discrete ionic catalysts.Transition metals include the lanthanide and actinide metals as well asGroup-3-10 metals. Transition-metal, olefin-polymerization catalysts arereferred to throughout this disclosure variously as transition-metal,olefin-polymerization catalysts; olefin-polymerization catalysts;polymerization catalysts; or simply as catalysts. Their correspondingcatalyst precursors are referred to similarly, e.g. transition metalolefin polymerization catalyst precursors.

Invention noncoordinating anions suit all ionic catalyst systems thatuse NCAs. Suitable transition metal catalysts include those transitionmetal compounds that polymerize olefins when activated to a cationicstate. Suitable processes include those run in homogeneous andheterogeneous, gas-phase, solution, slurry, and bulk polymerizationprocesses to make (co)polymers of ethylenically unsaturated monomer(s):ethylene, propylene, C₄-C₂₀ α-olefins, C₅-C₂₀ strained-ring cyclicolefins (e.g., norbomene, alkyl-substituted norbomenes), vinyl aromaticmonomers (e.g., styrene and alkyl-substituted styrenes), or macromer(s)derived from those monomers. Such processes typically operate from−50-250° C. and from 0-3000 bar.

An embodiment of an invention partially fluorinated activator issynthesized using the reaction shown below.

Preparing this borate complex from partially fluorinated naphthylligands proceeds at higher yields and at higher purities than complexformation using perfluorinated naphthyl ligands.

Group-4-6 metallocenes exemplify transition-metal, olefin-polymerizationcatalysts. Metallocenes include (un)bridged compounds containing one(mono(cyclopentadienyl)metallocenes) or two (bis(cyclopentadienyl)metallocenes)(un)substituted cyclopentadienyl ligand(s). In bridgedmetallocenes, a single, cyclopentadienyl ligand connects to a heteroatomligand with both coordinating to the metal center, or twocyclopentadienyl ligands connect together with both CP ligandscoordinating to the metal center. Typical catalysts and their precursorsare well known in the art. Suitable description appears in the patentliterature, for example U.S. Pat. Nos. 4,871,705, 4,937,299, 5,324,800,EP-A-0418044, EP-A-0591756, WO-A-92/00333 and WO-A-94/01471. Someembodiments select the metallocene compounds from mono- orbis-CP-substituted, Group-4, -5, and -6 metals in which CPs are(un)substituted with one or more groups or are bridged to each other orto a metal-coordinated heteroatom. Some embodiments select similarmetallocene compounds except they are not necessarily bridged to eachother or to a metal-coordinated heteroatom. Some higher-molecular-weightpolymer-producing embodiments employ bridged biscyclopentadienyl (orsubstituted biscyclopentadienyl (such as (un)substituted indenyl,(un)substituted fluorenyl, (un)substituted)azulenyl, etc.) rings, andare lower-alkyl-substituted (C₁-C₆) in the 2 position and additionallycontain alkyl, cycloalkyl, aryl, alkylaryl or arylalkyl substituents.Arylalkyl substituents appear either as fused- or pendant-ringstructures including multi-ring structures, for example, those of U.S.Pat. Nos. 5,278,264 and 5,304,614.

Metallocene compounds suitable for linear polyethylene orethylene-containing copolymer production (where copolymer meanscomprising at least two different monomers) are essentially thosedisclosed in WO-A-92/00333, WO 97/44370 and U.S. Pat. Nos. 5,001,205,5,057,475, 5,198,401, 5,304,614, 5,308,816 and 5,324,800. Selection ofmetallocene compounds for isotactic or syndiotactic polypropylene blendproduction, and their syntheses, are well-known in the patent andacademic literature, e.g. Journal of Organometallic Chemistry 369,359-370 (1989). Typically, those catalysts are stereorigid, asymmetric,chiral, or bridged-chiral metallocenes. Invention activators are suitedfor activating these types of catalyst precursors.

Likewise, invention activators are suited for activatingmonocyclopentadienyl metallocenes with Group-15 or -16 heteroatomsconnected, through a bridging group, to a Cp-ligand ring carbon Both theCp-ligand and the heteroatom connect to a transition metal. Someembodiments select a Group-4 transition metal. Additionally, unbridgedmonocyclopentadienyl, heteroatom-containing Group-4 components of WO97/22639 will function with this invention. Moreover, transition metalsystems with high-oxidation-state, Group-5-10 transition-metal centersare known. These are stabilized by high-oxidation-state,low-coordination-number polyanionic ligands. To the extent that thecatalyst precursors are NCA activable, they will function with inventionactivators, as well.

Non-cyclopentadienyl, Group-4-5 precursor compounds activable to stable,discrete cationic complexes include those containing bulky, chelating,diamide ligands, such as described in U.S. Pat. No. 5,318,935 and“Conformationally Rigid Diamide Complexes: Synthesis and Structure ofTantalum (III)Alkyne Derivatives”, D. H. McConville, et al,Organometallics 1995, 14, 3154-3156. U.S. Pat. No. 5,318,935 describesbridged and unbridged, bisamido catalyst compounds of Group-4 metalscapable of α-olefins polymerization. Bridged bis(arylamido)Group-4compounds for olefin polymerization are described by D. H. McConville,et al., in Organometallics 1995, 14, 5478-5480. Synthetic methods andcompound characterization are presented. Further work appearing in D. H.McConville, et al, Macromolecules 1996, 29, 5241-5243, describes bridgedbis(arylamido)Group-4 compounds that are polymerization catalysts for1-hexene. Additional invention-suitable transition-metal compoundsinclude those described in WO 96/40805. Cationic Group-3- or Lanthanideolefin polymerization complexes are disclosed in copending U.S.application Ser. No. 09/408050, filed 29 Sep. 1999, and its equivalentPCT/US99/22690. A monoanionic bidentate ligand and two monoanionicligands stabilize those catalyst precursors; they are activable withthis invention's ionic cocatalysts. Other suitable Group-4-5non-metallocene catalysts are bimetallocyclic catalyst compoundscomprising two independently selected Group-4-5 metal atoms directlylinked through two bridging groups to form cyclic compounds.

Suitable Group-10 compounds have a 2⁺ oxidation state. Typical Ni²⁺ andPd²⁺ complexes are diimines, see “New Pd(II)- and Ni(II)- BasedCatalysts for Polymerization of Ethylene and α-Olefins”, M. Brookhart,et al, J. Am. Chem. Soc., 1995, 117, 6414-6415, WO 96/23010 and WO97/02298. See additionally the related bis(imino)Group-8 and -9organometallic compounds described by V. C. Gibson and others in “Novelolefin polymerization catalysts based on iron and cobalt”, Chem.Commun., 849-850, 1998.

Conventional preparations of activetransition-metal-noncoordinating-anion catalyst systems are known.Typically, the methods comprise obtaining transition metal compoundswith abstractable ligands, e.g., hydride, alkyl or silyl group. Next,the transition metal compound is contacted with a noncoordinating anionor cocatalyst compound in a solvent. The cocatalyst abstracts theunivalent hydride, alkyl, or silyl ligand. Abstraction leaves thetransition metal compounds with an increased cationic charge, which iscounterbalanced by the noncoordinating anion. This activated catalystsystem can be introduced into the polymerization reactor in a variety ofways as is known in the art. Moreover, the catalyst precursor andactivator can also be contacted with each other inside of the reactor.

Invention noncoordinating anions may be introduced as either ioniccompounds having a cation that abstracts one catalyst precursor ligandby protonation or oxidation, or as neutral compounds that directlyabstract such a ligand to form a noncoordinating anion. Both ways createa noncoordinating anion. Additionally, alklylating agents can transformnon-NCA-abstractable ligands (e.g. transition metal dihalides) intoNCA-abstractable ones (e.g. transition metal alkyls). Typically, thestrongly Lewis acidic, organoaluminum compounds such as thelower-carbon-number alkyl aluminums and alkylalumoxanes serve asalkylating sources. In situ processes in which alkyl aluminum compoundsreact with dihalo-substituted metallocene compounds before or uponadding activating anion precursor compounds are known. Some embodimentsselect transition metal compounds without metal-center halides forcatalyst systems, since in situ alkylation may enable competingreactions and interactions that interfere with overall polymerizationefficiency under high temperature conditions.

Cation counterparts for invention noncoordinating anion salts includethose known in the art for NCAs. Various cation classes includenitrogen-containing cations such as in the anilinium and ammonium saltsof U.S. Pat. No. 5,198,401 and WO 97/35893; the carbenium, oxonium, orsulfonium cations of U.S. Pat. No. 5,387,568; metal cations, e.g., Ag⁺;the silylium cations of WO 96/08519; and those of the hydrated, Group-1or -2 metal cations of WO 97/22635. Additionally, invention NCAs cancome from neutral Lewis acids comprising a Group-13 metal or metalloidcenter and from one to three halogenated aryl ligands as described abovefor the invention. Complementary ligands are selected from those knownin the art for noncoordinating anions.

The activators of this invention are useful for metallocene catalystsystems that are themselves useful in the polymerization of all types ofolefins. This includes polymerization processes that producehomopolymers, copolymers, terpolymers and the like as well as blockcopolymers and impact copolymers. The polymerization or copolymerizationis carried out using olefins of the formula R^(a)CH═CH—R^(b). In thisformula, R^(a) and R^(b) are identical or different and equal a hydrogenatom or a 1-14-carbon-atom-alkyl radical. But R^(a) and R^(b) mayalternatively form a ring together with the carbon atoms connectingthem. Examples of such olefins are ethylene, propylene, 1-butene,1-hexene, 4-methyl-1-pentene, 1-octene, norbornene and norbornadiene. Inparticular, propylene and ethylene are polymerized.

Invention catalyst complexes are useful in polymerizing unsaturatedmonomers known to react under coordination polymerization conditionsusing metallocenes. For example, polymerization catalysts for olefinpolymerization, such as to prepare polyethylene, polypropylene, andcopolymers of each. Di-methylsilylbis(indenyl)hafnium dimethyl producescopolyethylene-polypropylene.Diphenylmethylene(cyclopentadienyl)(fluorenyl)hafnium dimethylpolymerizes octene into polyoctene when activated with inventionactivators. Such conditions are well known and include solution, slurry,gas-phase, and high-pressure polymerizations. Invention catalysts may besupported and, as such, will be particularly useful in the knownoperating modes employing fixed-bed, moving-bed, fluid-bed, slurry, orsolution processes conducted in single, series, or parallel reactors.

Numerous support methods for olefin copolymerization processes are knownin the art. Both inorganic oxide and polymeric supports may be used asknown in the art.

Methods for supporting ionic catalysts comprising metallocene cationsand NCA are described in WO 9950311; U.S. Pat. Nos. 5,643,847;5,972,823; 6,228,795; and 6,143,686.

Some embodiments first add the NCA to the support composition followedby the addition of the metallocene catalyst. Other methods and order ofaddition will be apparent to those skilled in the art.

The catalyst systems used to prepare the compositions of this inventionare sometimes supported using a porous particulate material, such as forexample, talc, inorganic oxides, inorganic chlorides such as magnesiumchloride, and resinous materials such as polyolefin or polymericcompounds.

Some embodiments select porous inorganic oxides as the supportmaterials. These oxides include Group-2, -3, -4, -5, -13 or -14metallmetalloid oxides. Silica, alumina, silica-alumina, and mixturesthereof specific, non-limiting examples of those oxides. Other inorganicoxides that may be employed either alone or in combination with thesilica, alumina, or silica-alumina are magnesia, titania, zirconia, andthe like.

Some embodiments select the support material as porous silica, which hasa surface area of 10-700 m²/g, a total pore volume of 0.1-4.0 cc/g andan average particle size of 10-500 μm. Other embodiments select thesurface area to be 50-500 m²/g, the pore volume to be 0.5-3.5 cc/g andthe average particle size to be 20-200 μm. Particularly, the surfacearea is 100-400 m²/g; the pore volume is 0.8-3.0 cc/g; and the averageparticle size is 30-100 μm. The average pore size of typical poroussupport materials is 10-1000 Å. Some embodiments select a supportmaterial that has an average pore diameter of 50-500 Å, and particularlyfrom 75-350 Å. The silica may be dehydrated at 100° C.-800° C. for from3-24 hours.

The metallocene, activator, and support material may be combined in anynumber of ways. More than one metallocene may also be used. Examples ofsuitable support techniques are described U.S. Pat. Nos. 4,808,561 and4,701,432. In some embodiments, the metallocenes and activator arecombined and their reaction product supported on the porous supportmaterial as described in U.S. Pat. No. 5,240,894 and WO 94/ 28034, WO96/00243, and WO 96/00245. Alternatively, the metallocenes may bepreactivated separately and then combined with the support materialeither separately or together. If the metallocenes are separatelysupported, they can be dried then combined as a powder before use inpolymerization.

Regardless of whether the metallocene(s) and their activator areseparately precontacted or whether the metallocene(s) and activator arecombined at once, some embodiments select the total volume of reactionsolution applied to the porous support to be less than 4 times the totalpore volume of the porous support, particularly less than 3 times thetotal pore volume of the porous support and more particularly from 1-2.5times the total pore volume of the porous support. Procedures formeasuring the total pore volume of porous support are well known in theart. One such method is described in Volume 1, Experimental Methods inCatalyst Research, Academic Press, 1968, pages 67-96.

The supported catalyst system may be used directly in polymerization orthe catalyst system may be prepolymerized using methods well known inthe art. For details regarding prepolymerization, see U.S. Pat. Nos.4,923,833 and 4,921,825, and EP 0 279 863 and EP 0 354 893.

When using invention catalysts, particularly when support immobilized,the catalyst system will generally additionally comprise one or morescavengers. The term “scavengers” means compounds that remove impuritiesfrom the reaction. These impurities adversely affect catalyst activityand stability. In most cases, purification steps are taken beforeintroducing the feeds into the reaction vessel. But small scavengingcompound amounts will normally be used in the polymerization process.Where possible, alkylaluminum scavenging compounds are avoidedaltogether.

Typically, the scavenger will be an organometallic compound such as theGroup-13 organometallic compounds of U.S. Pat. Nos. 5,153,157, 5,241,025and WO-A-91/09882, WO-A-94/03506, WO-A-93/14132, WO 95/07941 and of WO97/22635. Exemplary compounds include triethyl aluminum, triethylborane, triisobutyl aluminum, methylalumoxane, isobutyl aluminumoxane,tri(n-octyl) aluminum and tri(n-octyl)aluminum. Those scavengers havingbulky or C₆-C₂₀ linear hydrocarbyl substituents covalently bound to themetal or metalloid center usually to minimize adverse interaction withthe active catalyst. Examples include triethylaluminum, bulky compoundssuch as triisobutylaluminum, triisoprenylaluminum, and long-chainlinear-alkyl-substituted aluminum compounds, such astri-n-hexylaluminum, tri-n-octylaluminum, or tri-n-dodecylaluminum.Alumoxanes also may be used in scavenging amounts, e.g., methylalumoxaneand triisobutyl-aluminoxane. Invention processes minimize the scavengeramount during polymerization reactions to that amount effective toenhance activity and avoid them altogether if the feeds are sufficientlyimpurity free.

Some invention embodiments employ catalyst systems in liquid phase(solution, slurry, suspension, bulk phase or their combinations), inhigh-pressure-liquid or supercritical-fluid phase, or in gas phase.Singular, parallel, or series reactors suit these processes. The liquidprocesses comprise contacting olefin monomers with the describedcatalyst systems in suitable diluents or solvents and comprise allowingthose monomers to react long enough to produce invention copolymers,both aliphatic and aromatic ones. Hydrocarbyl solvents are suitable.Some embodiments select hexane and toluene. Halocarbon solvents, such asmethylene chloride are also suitable. Some embodiments use othersolvents such as aliphatic, cycloaliphatic or aromatic hydrocarbons.Some embodiments select solvents with C₁₂ or lower, straight-chain orbranched-chain, saturated hydrocarbons, and C₅-C₉, saturated alicyclicor aromatic hydrocarbons. Examples of such solvents or reaction mediaare hexane, butane, pentane, heptane, cyclopentane, cyclohexane,cycloheptane, methyl cyclopentane, methyl cyclohexane, isooctane,benzene, toluene, xylene and their mixtures. In addition, one or moreolefins, either alone or mixed with other media, may serve as thereaction media, at selected olefin concentrations. Bulk and slurryprocesses typically include contacting the catalysts supported withliquid monomer or with monomer in liquid alkane.

Gas-phase coordination polymerizations typically use a supported cata-lyst and are conducted in any suitable manner for ethylene homo- orco-polymerization.

Generally speaking, polymerization reaction temperatures vary from −50°C.-250° C. Some embodiments select the reaction temperature from −20°C.-220°; other embodiments select the reaction temperature below 200° C.Pressure ranges from about 0.001-3000 bar. Some embodiments selectpressure from 0.1 bar-2000 bar. Molecular weight, tacticity, and stereo-and regio-defect levels depend on reactor temperature. Thus, desiredvalues for these properties guide reactor temperature selection. Thereactors may be cooled by reactor jackets, cooling coils, autorefrigeration, pre-chilled feeds, or their combinations. Someembodiments select adiabatic reactors with pre-chilled feeds.

In some embodiments, processes using unsupported catalysts are designedor conducted such that the transition metal compounds and the anionprecursor compounds are kept apart. They are mixed in the reactor orimmediately before reactor injection. An example is dual injection ofeach catalyst component directly into the reactor. Another is premixingwith T- or multi-joint mixing chambers just before reactor injection.Alternatively, some embodiments employ in-situ-formed catalyst preparedby adding ionic activator, ligand-stabilized metal-halide catalystprecursor, and scavenger directly into the reactor or into the T- ormulti-joint mixing chambers for pre-injection preparation. Someembodiments call for scavenger injection separate from catalyst systemor catalyst compound injection.

The following metallocene catalysts are activable by invention partiallyfluorinated discrete activators:

-   -   (benzylcyclopentadienyl)(cyclopentadienyl)hafnium dihydride;        (benzylcyclopentadienyl)(cyclopentadienyl)hafnium dimethyl;        (benzylcyclopentadienyl)(cyclopentadienyl)titanium dihydride;        (benzylcyclopentadienyl)(cyclopentadienyl)titanium dimethyl;        (benzylcyclopentadienyl)(cyclopentadienyl)zirconium dihydride;        (benzylcyclopentadienyl)(cyclopentadienyl)zirconium dimethyl;        (cyclohexylmethylcyclopentadienyl) (cyclopentadienyl)hafnium        dimethyl;        (cyclohexylmethylcyclopentadienyl)(cyclopentadienyl)titanium        dimethyl;        (cyclohexylmethylcyclopentadienyl)(cyclopentadienyl)zirconium        dimethyl;        (cyclohexylmethylcyclopentadienyl)(cyclopentadienyl)hafnium        dihydride;        (cyclohexylmethylcyclopentadienyl)(cyclopentadienyl)titanium        dihydride;        (cyclohexylmethylcyclopentadienyl)(cyclopentadienyl)zirconium        dihydride; (dimethylcyclopentadienyl)(cyclopentadienyl)hafnium        dihydride; (dimethylcyclopentadienyl)(cyclopentadienyl)hafnium        dimethyl; (dimethylcyclopentadienyl)(cyclopentadienyl)titanium        dihydride; (dimethylcyclopentadienyl)(cyclopentadienyl)titanium        dimethyl; (dimethylcyclopentadienyl)(cyclopentadienyl)zirconium        dihydride; (dimethylcyclopentadienyl)(cyclopentadienyl)zirconium        dimethyl;        (diphenylmethylcyclopentadienyl)(cyclopentadienyl)hafnium        dimethyl;        (diphenylmethylcyclopentadienyl)(cyclopentadienyl)titanium        dimethyl;        (diphenylmethylcyclopentadienyl)(cyclopentadienyl)zirconium        dimethyl;        (diphenylmethylcyclopentadienyl)(cyclopentadienyl)hafnium        dihydride;        (diphenylmethylcyclopentadienyl)(cyclopentadienyl)titanium        dihydride;        (diphenylmethylcyclopentadienyl)(cyclopentadienyl)zirconium        dihydride; (ethylcyclopentadienyl)(cyclopentadienyl)hafnium        dimethyl; (ethylcyclopentadienyl)(cyclopentadienyl)titanium        dimethyl; (ethylcyclopentadienyl)(cyclopentadienyl)zirconium        dimethyl; (ethylcyclopentadienyl)(cyclopentadienyl)hafnium        dihydride; (ethylcyclopentadienyl)(cyclopentadienyl)titanium        dihydride; (ethylcyclopentadienyl)(cyclopentadienyl)zirconium        dihydride; (ethyltetramethylcyclopentadienyl)        (cyclopentadienyl)hafnium dihydride;        (ethyltetramethylcyclopentadienyl)(cyclopentadienyl)hafnium        dimethyl;        (ethyltetramethylcyclopentadienyl)(cyclopentadienyl)titanium        dihydride;        (ethyltetramethylcyclopentadienyl)(cyclopentadienyl)titanium        dimethyl;        (ethyltetramethylcyclopentadienyl)(cyclopentadienyl)zirconium        dihydride;        (ethyltetramethylcyclopentadienyl)(cyclopentadienyl)zirconium        dimethyl; (indenyl)(cyclopentadienyl)hafnium dihydride;        (indenyl)(cyclopentadienyl)hafnium dimethyl;        (indenyl)(cyclopentadienyl)titanium dihydride;        (indenyl)(cyclopentadienyl)titanium dimethyl;        (indenyl)(cyclopentadienyl)zirconium dihydride;        (indenyl)(cyclopentadienyl)zirconium dimethyl;        (methylcyclopentadienyl)(cyclopentadienyl)hafnium dihydride;        (methylcyclopentadienyl)(cyclopentadienyl)hafnium dimethyl;        (methylcyclopentadienyl) (cyclopentadienyl)titanium dihydride;        (methylcyclopentadienyl)(cyclopentadienyl)titanium dimethyl;        (methylcyclopentadienyl)(cyclopentadienyl)zirconium dihydride;        (methylcyclopentadienyl)(cyclopentadienyl)zirconium dimethyl;        (n-butylcyclopentadienyl)(cyclopentadienyl)hafnium dimethyl;        (n-butylcyclopentadienyl)(cyclopentadienyl)titanium dimethyl;        (n-butylcyclopentadienyl) (cyclopentadienyl)zirconium dimethyl;        (n-butylcyclopentadienyl)(cyclopentadienyl)hafnium dihydride;        (n-butylcyclopentadienyl)(cyclopentadienyl)titanium dihydride;        (n-butylcyclopentadienyl)(cyclopentadienyl)zirconium dihydride;        (pentamethylcy-clopentadienyl) (cyclopentadienyl)hafnium        dihydride;        (pentamethylcyclopentadienyl)(cyclopentadienyl)hafnium dimethyl;        (pentamethylcyclopentadienyl)(cyclopentadienyl)titanium        dihydride;        (pentamethylcyclopentadienyl)(cyclopentadienyl)titanium        dimethyl;        (pentamethylcyclopentadienyl)(cyclopentadienyl)zirconium        dihydride;        (pentamethylcyclopentadienyl)(cyclopentadienyl)zirconium        dimethyl; (propylcyclopentadienyl)(cyclopentadienyl)hafnium        dimethyl; (propylcyclopentadienyl)(cyclopentadienyl)titanium        dimethyl; (propylcyclopentadienyl)(cyclopentadienyl)zirconium        dimethyl; (propylcyclopentadienyl)(cyclopentadienyl)hafnium        dihydride; (propylcyclopentadienyl)(cyclopentadienyl)titanium        dihydride; (propylcyclopentadienyl)(cyclopentadienyl)zirconium        dihydride; (t-butylcyclopentadienyl)(cyclopentadienyl)hafnium        dimethyl; (t-butylcyclopentadienyl)(cyclopentadienyl)titanium        dimethyl; (t-butylcyclopentadienyl)(cyclopentadienyl)zirconium        dimethyl; (t-butylcyclopentadienyl)(cyclopentadienyl)hafnium        dihydride; (t-butylcyclopentadienyl)(cyclopentadienyl)titanium        dihydride; (t-butylcyclopentadienyl)(cyclopentadienyl)zirconium        dihydride; (tetramethylcyclopentadienyl)        (cyclopentadienyl)hafnium dihydride;        (tetramethylcyclopentadienyl)(cyclopentadienyl)hafnium dimethyl;        (tetramethylcyclopentadienyl)(cyclopentadienyl)titanium        dihydride;        (tetramethylcyclopentadienyl)(cyclopentadienyl)titanium        dimethyl;        (tetramethylcyclopentadienyl)(cyclopentadienyl)zirconium        dihydride;        (tetramethylcyclopentadienyl)(cyclopentadienyl)zirconium        dimethyl; (trifluoromethylcyclopentadienyl)(cyclopentadienyl)        hafnium dihydride;        (trifluoromethylcyclopentadienyl)(cyclopentadienyl)titanium        dihydride;        (trifluoromethylcyclopentadienyl)(cyclopentadienyl)zirconium        dihydride;        (trifluoromethylcyclopentadienyl)(cyclopentadienyl)hafnium        dimethyl;        (trifluoromethylcyclopentadienyl)(cyclopentadienyl)titanium        dimethyl;        (trifluoromethylcyclopentadienyl)(cyclopentadienyl)zirconium        dimethyl; (trimethylcyclopentadienyl)(cyclopentadienyl)hafnium        dihydride; (trimethylcyclopentadienyl) (cyclopentadienyl)hafnium        dimethyl; (trimethylcyclopentadienyl) (cyclopentadienyl)titanium        dihydride; (trimethylcyclopentadienyl)(cyclopentadienyl)titanium        dimethyl; (trimethylcyclopentadienyl)(cyclopentadienyl)zirconium        dihydride;        (trimethylcyclopentadienyl)(cyclopentadienyl)zirconium dimethyl;        (trimethylgermylcyclopentadienyl)(cyclopentadienyl)hafnium        dihydride;        (trimethylgermylcyclopentadienyl)(cyclopentadienyl)titanium        dihydride; (trimethylgermylcyclopentadienyl)        (cyclopentadienyl)zirconium dihydride;        (trimethylgermylcyclopentadienyl)(cyclopentadienyl)hafnium        dimethyl;        (trimethylgermylcyclopentadienyl)(cyclopentadienyl)titanium        dimethyl;        (trimethylgermylcyclopentadienyl)(cyclopentadienyl)zirconium        dimethyl; (trimethylplumbylcyclopentadienyl)        (cyclopentadienyl)hafnium dihydride;        (trimethylplumbylcyclopentadienyl)(cyclopentadienyl)titanium        dihydride;        (trimethylplumbylcyclopentadienyl)(cyclopentadienyl)zirconium        dihydride;        (trimethylplumbylcyclopentadienyl)(cyclopentadienyl)hafnium        dimethyl;        (trimethylplumbylcyclopentadienyl)(cyclopentadienyl)titanium        dimethyl;        (trimethylplumnbylcyclopentadienyl)(cyclopentadienyl)zirconium        dimethyl;        (trimethylsilylcyclopentadienyl)(cyclopentadienyl)hafnium        dihydride;        (trimethylsilylcyclopentadienyl)(cyclopentadienyl)hafnium        dimethyl;        (trimethylsilylcyclopentadienyl)(cyclopentadienyl)titanium        dihydride;        (trimethylsilylcyclopentadienyl)(cyclopentadienyl)titanium        dimethyl;        (trimethylsilylcyclopentadienyl)(cyclopentadienyl)zirconium        dihydride;        (trimethylsilylcyclopentadienyl)(cyclopentadienyl)zirconium        dimethyl;        (trimethylstannylcyclopentadienyl)(cyclopentadienyl)hafnium        dihydride;        (trimethylstannylcyclopentadienyl)(cyclopentadienyl)titanium        dihydride;        (trimethylstannylcyclopentadienyl)(cyclopentadienyl)zirconium        dihydride;        [1,1′-(1,1,2,2-tetramethyldisilanylene)bis(3-methylcyclopentadienyl)]zirconium        dimethyl;        [1,1′-(1,1,2,2-tetramethyldisilanylene)bis(3-trimethylsilanylcyclopentadienyl)]zirconium        dimethyl;        [1,1′-(1,1,2,2-tetramethyldisilanylene)-bis(4,5,6,7-tetrahydroindenyl)]hafnium        dimethyl;        [1,1′-(1,1,2,2-tetramethyldisilanylene)-bis(4,5,6,7-tetrahydroindenyl)]titanium        dimethyl;        [1,1′-(1,1,2,2-tetramethyldisilanylene)-bis(4,5,6,7-tetrahydroindenyl)]zirconium        dimethyl;        [1,1′-(1,1,3,3-tetramethyldisiloxanylene)bis(4,5,6,7-tetrahydroindenyl)]hafnium        dimethyl;        [1,1′-(1,1,3,3-tetramethyldisiloxanylene)bis(4,5,6,7-tetrahydroindenyl)]titanium        di-methyl;        [1,1′-(1,1,3,3-tetramethyldisiloxanylene)bis(4,5,6,7-tetrahydroindenyl)]zirconium        dimethyl;        [1,1′-(1,1,4,4-tetramethyl-1,4-disilanylbutylene)bis(4,5,6,7-tetrahydroindenyl)]hafnium        dimethyl;        [1,1′-(1,1,4,4-tetramethyl-1,4-disilanylbutylene)bis(4,5,6,7-tetrahydroindenyl)]titanium        dimethyl;        [1,1′-(1,1,4,4-tetramethyl-1,4-disilanylbutylene)bis(4,5,6,7-tetrahydroindenyl)]zirconium        di-methyl;        [1,1′-(2,2-dimethyl-2-silapropylene)-bis(3-methylcyclopentadienyl)]hafnium        dimethyl;        [1,1′-(2,2-dimethyl-2-silapropylene)-bis(3-methylcyclopentadienyl)]titanium        dimethyl;        [1,1′-(2,2-dimethyl-2-silapropylene)-bis(3-methylcyclopentadienyl)]zirconium        dimethyl;        [1,1′-dimethylsilanylenebis(3-methylcyclopentadienyl)]hafnium        dimethyl;        [1,1′-dimethylsilanylenebis(3-methylcyclopentadienyl)]titanium        dimethyl;        [1,1′-dimethylsilanylenebis(3-methylcyclopentadienyl)]zirconium        dimethyl;        [1,1′-dimethylsilanylene-bis(3-trimethylsilanylcyclopentadienyl)]hafnium        dimethyl;        [1,1′-dimethylsilanylene-bis(3-trimethylsilanylcyclopentadienyl)]titanium        dimethyl;        [1,1′-dimethylsilanylene-bis(3-trimethylsilanylcyclopentadienyl)]zirconium        dimethyl;        [1,1′-dimethylsilanylene-bis(4,5,6,7-tetrahydroindenyl)]hafnium        dimethyl;        [1,1′-dimethylsilanylene-bis(4,5,6,7-tetrahydroindenyl)]titanium        dimethyl;        [1,1′-dimethylsilanylene-bis(4,5,6,7-tetrahydroindenyl)]zirconium        dimethyl; [1,1′-dimethylsilanylene-bis(indenyl)]hafnium        dimethyl; [1,1′-dimethylsilanylene-bis(indenyl)]titanium        dimethyl; [1,1′-dimethylsilanylenebis(indenyl)]zirconium        dimethyl; bis(benzylcyclopentadienyl)hafnium dihydride;        bis(benzylcyclopentadienyl)hafnium dimethyl;        bis(benzylcyclopentadienyl)titanium dihydride;        bis(benzylcyclopentadienyl)titanium dimethyl;        bis(benzylcyclopentadienyl)zirconium dihydride;        bis(benzylcyclopentadienyl)zirconium dimethyl;        bis(cyclohexylmethylcyclopentadienyl)hafnium dihydride;        bis(cyclohexylmethylcyclopentadienyl)hafnium dimethyl;        bis(cyclohexylmethylcyclopentadienyl)titanium dihydride;        bis(cyclohexylmethylcyclopentadienyl)titanium dimethyl;        bis(cyclohexylmethylcyclopentadienyl)zirconium dihydride;        bis(cyclohexylmethylcyclopentadienyl)zirconium dimethyl;        bis(cyclopentadienyl)(trimethylsilyl)(methyl)hafnium;        bis(cyclopentadienyl)(trimethylsilyl)(methyl)titanium;        bis(cyclopentadienyl)(trimethylsilyl)(methyl)zirconium;        bis(cyclopentadienyl)[tris(dimethylsilyl)silyl](methyl)hafnium;        bis(cyclopentadienyl)[tris(dimethylsilyl)silyl](methyl)titanium;        bis(cyclopentadienyl)[tris(dimethylsilyl)silyl](methyl)zirconium;        bis(cyclopentadienyl)(trimethylsilyl)(tris(trimethylsilyl)(trimethylsilylbenzyl);        bis(cyclopentadienyl)(triphenylsilyl)(methyl)hafnium;        bis(cyclopentadienyl)(triphenylsilyl)(methyl)titanium;        bis(cyclopentadienyl)(triphenylsilyl)(methyl)zirconium;        bis(cyclopentadienyl)hafnium di(m-tolyl);        bis(cyclopentadienyl)hafnium di(p-tolyl);        bis(cyclopentadienyl)hafnium dibutyl;        bis(cyclopentadienyl)hafnium diethyl;        bis(cyclopentadienyl)hafnium dihydride;        bis(cyclopentadienyl)hafnium dimethyl;        bis(cyclopentadienyl)hafnium dineopentyl;        bis(cyclopentadienyl)hafnium diphenyl;        bis(cyclopentadienyl)hafnium dipropyl;        bis(cyclopentadienyl)titanium di(m-tolyl);        bis(cyclopentadienyl)titanium di(p-tolyl);        bis(cyclopentadienyl)titanium dibutyl;        bis(cyclopentadienyl)titanium diethyl;        bis(cyclopentadienyl)titanium dihydride;        bis(cyclopentadienyl)titanium dimethyl;        bis(cyclopentadienyl)titanium dineopentyl;        bis(cyclopentadienyl)titanium diphenyl;        bis(cyclopentadienyl)titanium dipropyl;        bis(cyclopentadienyl)zirconium di(m-tolyl);        bis(cyclopentadienyl)zirconium di(p-tolyl);        bis(cyclopentadienyl)zirconium dibutyl;        bis(cyclopentadienyl)zirconium diethyl;        bis(cyclopentadienyl)zirconium dihydride;        bis(cyclopentadienyl)zirconium dimethyl;        bis(cyclopentadienyl)zirconium dineopentyl;        bis(cyclopentadienyl)zirconium diphenyl;        bis(cyclopentadienyl)zirconium dipropyl;        bis(dimethylcyclopentadienyl)hafnium dihydride;        bis(dimethylcyclopentadienyl)hafnium dimethyl;        bis(dimethylcyclopentadienyl)titanium dihydride;        bis(dimethylcyclopentadienyl)titanium dimethyl;        bis(dimethylcyclopentadienyl)zirconium dihydride;        bis(dimethylcyclopentadienyl)zirconium dimethyl;        bis(diphenylmethylcyclopentadienyl)hafnium dihydride;        bis(diphenylmethylcyclopentadienyl)hafnium dimethyl;        bis(diphenylmethylcyclopentadienyl)titanium dihydride;        bis(diphenylmethylcyclopentadienyl)titanium dimethyl;        bis(diphenylmethylcyclopentadienyl)zirconium dihydride;        bis(diphenylmethylcyclopentadienyl)zirconium dimethyl;        bis(ethylcyclopentadienyl)hafnium dimethyl;        bis(ethylcyclopentadienyl)titanium dimethyl;        bis(ethylcyclopentadienyl)zirconium dimethyl;        bis(ethyltetramethylcyclopentadienyl)hafnium dimethyl;        bis(ethyltetramethylcyclopentadienyl)titanium dimethyl;        bis(ethyltetramethylcyclopentadienyl)zirconium dimethyl;        bis(ethyltetramethylcyclopentadienyl)hafnium dihydride;        bis(ethyltetramethylcyclopentadienyl)titanium dihydride;        bis(ethyltetramethylcyclopentadienyl)zirconium dihydride;        bis(indenyl)hafnium dihydride; bis(indenyl)hafnium dimethyl;        bis(indenyl)titanium dihydride; bis(indenyl)titanium dimethyl;        bis(indenyl)zirconium dihydride; bis(indenyl)zirconium dimethyl,        bis(methylcyclopentadienyl)hafnium dimethyl;        bis(methylcyclopentadienyl)titanium dimethyl;        bis(methylcyclopentadienyl)zirconium dimethyl;        bis(methylcyclopentadienyl)hafnium dihydride;        bis(methylcyclopentadienyl)titanium dihydride;        bis(methylcyclopentadienyl)zirconium dihydride;        bis(n-butylcyclopentadienyl)hafnium dimethyl;        bis(n-butylcyclopentadienyl)titanium dimethyl;        bis(n-butylcyclopentadienyl)zirconium dimethyl;        bis(n-butylcyclopentadienyl)hafnium dihydride;        bis(n-butylcyclopentadienyl)titanium dihydride;        bis(n-butylcyclopentadienyl)zirconium dihydride;        bis(pentamethylcyclopentadienyl)(benzyne)hafnium;        bis(pentamethylcyclopentadienyl)(benzyne)titanium;        bis(pentamethylcyclopentadienyl)(benzyne)zirconium;        bis(pentamethylcyclopentadienyl)hafnium dimethyl;        bis(pentamethylcyclopentadienyl)titanium dimethyl;        bis(pentamethylcyclopentadienyl)zirconacyclopentane;        bis(pentamethylcyclopentadienyl)zirconium dimethyl;        bis(pentamethylcyclopentadienyl)hafnium (methyl)(hydride);        bis(pentamethylcyclopentadienyl)hafnium (phenyl)(hydride);        bis(pentamethylcyclopentadienyl)hafnium dihydride;        bis(pentamethylcyclopentadienyl)titanium (methyl)(hydride);        bis(pentamethylcyclopentadienyl)titanium (phenyl)(hydride);        bis(pentamethylcyclopentadienyl)titanium dihydride;        bis(pentamethylcyclopentadienyl)zirconacyclobutane;        bis(pentamethylcyclopentadienyl)zirconium (methyl)(hydride);        bis(pentamethylcyclopentadienyl)zirconium (phenyl)(hydride);        bis(pentamethylcyclopentadienyl)zirconium dihydride;        bis(propylcyclopentadienyl)hafnium dimethyl;        bis(propylcyclopentadienyl)titanium dimethyl;        bis(propylcyclopentadienyl)zirconium dimethyl;        bis(propylcyclopentadienyl)hafnium dihydride;        bis(propylcyclopentadienyl)titanium dihydride;        bis(propylcyclopentadienyl)zirconium dihydride;        bis(t-butylcyclopentadienyl)hafnium dimethyl;        bis(t-butylcyclopentadienyl)titanium dimethyl;        bis(t-butylcyclopentadienyl)zirconium dimethyl;        bis(t-butylcyclopentadienyl)hafnium dihydride;        bis(t-butylcyclopentadienyl)titanium dihydride;        bis(t-butylcyclopentadienyl)zirconium dihydride;        bis(tetramethylcyclopentadienyl)hafnium dihydride;        bis(tetramethylcyclopentadienyl)hafnium dimethyl;        bis(tetramethylcyclopentadienyl)titanium dihydride;        bis(tetramethylcyclopentadienyl)titanium dimethyl;        bis(tetramethylcyclopentadienyl)zirconium dihydride;        bis(tetramethylcyclopentadienyl)zirconium dimethyl;        bis(trifluoromethylcyclopentadienyl)hafnium dihydride;        bis(trifluoromethylcyclopentadienyl)hafnium dimethyl;        bis(trifluoromethylcyclopentadienyl)titanium dihydride;        bis(trifluoromethylcyclopentadienyl)titanium dimethyl;        bis(trifluoromethylcyclopentadienyl)zirconium dihydride;        bis(trifluoromethylcyclopentadienyl)zirconium dimethyl;        bis(trimethylcyclopentadienyl)hafnium dihydride;        bis(trimethylcyclopentadienyl)hafnium dimethyl;        bis(trimethylcyclopentadienyl)titanium dihydride;        bis(trimethylcyclopentadienyl)titanium dimethyl;        bis(trimethylcyclopentadienyl)zirconium dihydride;        bis(trimethylcyclopentadienyl)zirconium dimethyl;        bis(trimethylgermylcyclopentadienyl)hafnium dihydride;        bis(trimethylgermylcyclopentadienyl)hafnium dimethyl;        bis(trimethylgermylcyclopentadienyl)titanium dihydride;        bis(trimethylgermylcyclopentadienyl)titanium dimethyl;        bis(trimethylgermylcyclopentadienyl)zirconium dihydride;        bis(trimethylgermylcyclopentadienyl)zirconium dimethyl;        bis(trimethylplumbylcyclopentadienyl)hafnium dihydride;        bis(trimethylplumbylcyclopentadienyl)hafnium dimethyl;        bis(trimethylplumbylcyclopentadienyl)titanium dihydride;        bis(trimethylplumbylcyclopentadienyl)titanium dimethyl;        bis(trimethylplumbylcyclopentadienyl)zirconium dihydride;        bis(trimethylplumbylcyclopentadienyl)zirconium dimethyl;        bis(trimethylsilylcyclopentadienyl)hafnium dihydride;        bis(trimethylsilylcyclopentadienyl)hafnium dimethyl;        bis(trimethylsilylcyclopentadienyl)titanium dihydride;        bis(trimethylsilylcyclopentadienyl)titanium dimethyl;        bis(trimethylsilylcyclopentadienyl)zirconium dihydride;        bis(trimethylsilylcyclopentadienyl)zirconium dimethyl;        bis(trimethylstannylcyclopentadienyl)hafnium dihydride;        bis(trimethylstannylcyclopentadienyl)titanium dihydride;        bis(trimethylstannylcyclopentadienyl)zirconium dihydride;        dibutylsilyl (fluorenyl) (cyclopentadienyl)hafnium dimethyl;        diethylsilanediylbis-(2-methylindenyl)-zirconium diethyl,;        diethylsilanediylbis-(2-methylindenyl)-zirconium dimethyl,;        dimethylsilanediylbis-(2-ethyl-5-isopropylcyclopentadienyl)-zirconium        dimethyl,; dimethylsilanediylbis-(2-ethylindenyl)-zirconium        dimethyl,; dimethylsilanediyl-bis-(2-isopropylindenyl)-zirconium        dimethyl,; dimethylsilanediylbis-(2-methyl-5-        ethylcyclopentadienyl)-zirconium dimethyl,;        dimethylsilanediylbis-(2-methyl-5-methylcyclopentadienyl)-zirconium        dimethyl,; dimethylsilanediylbis-(2-methylbenzindenyl)-zirconium        dimethyl; dimethylsilanediylbis-(2-methylindanyl)-zirconium        dimethyl,; dimethylsilanediylbis-(2-methylindenyl)-hafnium        dimethyl.; dimethylsilanediylbis-(2-methylindenyl)-zirconium        dimethyl,; dimethylsilanediylbis-(2-tert-butylindenyl)-zirconium        dimethyl,; dimethylsilyl (indenyl)(fluorenyl)hafnium dihydride;        dimethylsilyl bis(2-methyl-indenyl)hafnium dimethyl;        dimethylsilyl bis(2-propyl-indenyl)hafnium dimethyl;        dimethylsilyl bis(4-methyl, 2-phenyl-indenyl)hafnium dimethyl;        dimethylsilyl bis(cyclopentadienyl)hafnium dihydride;        dimethylsilyl bis(cyclopentadienyl)titanium dihydride;        dimethylsilyl bis(cyclopentadienyl)zirconium dihydride;        dimethylsilyl bis(indenyl)hafnium dimethyl;        dimethylsilyl(methylcyclopentadienyl)(1-fluorenyl)hafnium        dihydride;        dimethylsilyl(methylcyclopentadienyl)(1-fluorenyl)titanium        dihydride;        dimethylsilyl(methylcyclopentadienyl)(1-fluorenyl)zirconium        dihydride;        dimethylsilylbis(3-trimethylsilylcyclopentadienyl)hafnium        dihydride;        dimethylsilylbis(3-trimethylsilylcyclopentadienyl)titanium        dihydride;        dimethylsilylbis(3-trimethylsilylcyclopentadienyl)zirconium        dihydride; dimethylsilylbis(indenyl)hafnium dimethyl;        dimethylsilylbis(indenyl)titanium dimethyl;        dimethylsilylbis(indenyl)zirconium dimethyl;        dimethylthiobis-(2-methylindenyl)-zirconium dimethyl,;        dinapthylmethylene (cyclopentadienyl)(fluorenyl)hafnium        dimethyl; diphenylmethylene (2,7-di-n-butyl        fluorenyl)(cyclopentadienyl)hafnium dimethyl; diphenylmethylene        (2,7-di-n-butyl fluorenyl)(fluorenyl)hafnium dimethyl;        diphenylmethylene (2,7-di-t-butyl        fluorenyl)(cyclopentadienyl)hafnium dimethyl; diphenylmethylene        (2,7-di-t-butyl fluorenyl)(fluorenyl)hafnium dimethyl;        diphenylmethylene        (2,7-di-t-butyl-5-methylfluorenyl)(cyclopentadienyl)hafnium        dimethyl; diphenylmethylene (cyclopentadienyl)(2,7-dimethyl        fluorenyl)hafnium dimethyl; diphenylmethylene        (cyclopentadienyl)(2,7-di-t-butyl fluorenyl)hafnium dimethyl;        diphenylmethylene (indenyl)(2,7-di-t-butyl fluorenyl)hafnium        dibenzyl; ethylene bis(cyclopentadienyl)hafnium dihydride;        ethylene bis(cyclopentadienyl)hafnium dihydride; dimethylsilyl        bis(cyclopentadienyl)hafnium dihydride; ethylene        bis(cyclopentadienyl)hafnium dimethyl; ethylene        bis(cyclopentadienyl)titanium dihydride; ethylene        bis(cyclopentadienyl)titanium dihydride; dimethylsilyl        bis(cyclopentadienyl)titanium dihydride; ethylene        bis(cyclopentadienyl)titanium dimethyl; ethylene        bis(cyclopentadienyl)zirconium dihydride; ethylene        bis(cyclopentadienyl)zirconium dihydride; ethylene        bis(cyclopentadienyl)zirconium dimethyl;        ethylenebis(indenyl)hafnium dimethyl;        ethylenebis(indenyl)titanium dimethyl;        ethylenebis(indenyl)zirconium dimethyl;        ethylenebis(tetrahydroindenyl)hafnium dimethyl;        ethylenebis(tetrahydroindenyl)titanium dimethyl;        ethylenebis(tetrahydroindenyl)zirconium dimethyl; i-propyl        (cyclopentadienyl)(fluorenyl)hafnium dimethyl;        isopropyl(cyclopentadienyl)(1-fluorenyl)hafnium dimethyl;        isopropyl(cyclopentadienyl)(1-fluorenyl)titanium dimethyl;        isopropyl(cyclopentadienyl)(1-fluorenyl)zirconium dimethyl;        isopropyl(cyclopentadienyl)(1-octahydro-fluorenyl)hafnium        dimethyl;        isopropyl(cyclopentadienyl)(1-octahydro-fluorenyl)titanium        di&ethyl;        isopropyl(cyclopentadienyl)(1-octahydro-fluorenyl)zirconium        dimethyl; methylene (2,7-di-t-butyl fluorenyl)(fluorenyl)hafnium        dimethyl; methylene (indenyl)(2,7-di-t-butyl-fluorenyl)hafnium        dimethyl; methylene bis(cyclopentadienyl)hafnium dimethyl;        methylene bis(cyclopentadienyl)titanium dimethyl; methylene        bis(cyclopentadienyl)zirconium dimethyl; methylene        bis(fluorenyl)hafnium dimethyl; methylene(cyclopetadienyl        (tetramethylcyclopentadienyl)hafnium dimethyl;        methylene(cyclopentadienyl (tetramethylcyclopentadienyl)titanium        dimethyl; methylene(cyclopentadienyl        (tetramethylcyclopentadienyl)zirconium dimethyl;        methylene(cyclopentadienyl)(1-fluorenyl)hafnium dihydride;        methylene(cyclopentadienyl)(1-fluorenyl)titanium dihydride;        methylene(cyclopentadienyl)(1-fluorenyl)zirconium dihydride;        methylphenylmethylene bis(fluorenyl)hafnium dimethyl;        bis(methylcyclopentadienyl)zirconium dimethyl;        bis(ethylcyclopentadienyl)zirconium dimethyl;        bis(methylcyclopentadienyl)zirconium dimethyl;        bis(ethylcyclopentadienyl)zirconium dimethyl;        bis(methylcyclopentadienyl)zirconium dihydride;        bis(ethylcyclopentadienyl)zirconium dihydride;        bis(dimethylcyclopentadienyl)zirconium dimethyl;        bis(trimethylcyclopentadienyl)zirconium dimethyl;        bis(tetramethylcyclopentadienyl)zirconium dimethyl;        bis(ethyltetramethylcyclopentadienyl)zirconium dimethyl;        bis(indenyl)zirconium dimethyl;        bis(dimethylcyclopentadienyl)zirconium dimethyl;        bis(trimethylcyclopentadienyl)zirconium dimethyl;        bis(tetramethylcyclopentadienyl)zirconium dimethyl;        bis(ethyltetramethylcyclopentadienyl)zirconium dimethyl;        bis(indenyl)zirconium dimethyl;        bis(dimethylcyclopentadienyl)zirconium dihydride;        bis(trimethylcyclopentadienyl)zirconium dihydride;        bis(ethyltetramethylcyclopentadienyl)zirconium dihydride;        bis(trimethylsilylcyclopentadienyl)zirconium dimethyl;        bis(trimethylsilylcyclopentadienyl)zirconium dihydride;        bis(trifluoromethylcyclopentadienyl)zirconium dimethyl;        bis(trifluoromethylcyclopentadienyl)zirconium dimethyl;        bis(trifluoromethylcyclopentadienyl)zirconium dihydride;        isopropylidenebis(indenyl)zirconium dimethyl;        isopropylidene-bis(indenyl)zirconium dimethyl;        isopropylidene-bis(indenyl)zirconium dihydride;        pentamethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;        pentamethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;        pentamethylcyclopentadienyl(cyclopentadienyl)zirconium        dihydride;        ethyltetramethylcyclopentadienyl(cyclopentadienyl)zirconium        dihydride; isopropylidene(cyclopentadienyl)(fluorenyl)zirconium        dimethyl; isopropylidene(cyclopentadienyl)(fluorenyl)zirconium        dimethyl; dimethylsilyl(cyclopentadienyl)(fluorenyl)zirconium        dimethyl; isopropylidene(cyclopentadienyl)(fluorenyl)zirconium        dihydride, bis(cyclopentadienyl)zirconium dimethyl;        bis(cyclopentadienyl)zirconium dimethyl;        bis(cyclopentadienyl)zirconium diethyl;        bis(cyclopentadienyl)zirconium dipropyl;        bis(cyclopentadienyl)zirconium diphenyl;        methylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;        ethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;        methylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;        ethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;        methylcyclopentadienyl(cyclopentadienyl)zirconium dihydride;        ethylcyclopentadienyl(cyclopentadienyl)zirconium dihydride;        dimethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;        trimethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;        tetramethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;        bis(pentamethylcyclopentadienyl)zirconium dimethyl;        tetramethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;        indenyl(cyclopentadienyl)zirconium dimethyl;        dimethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;        trimethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;        tetramethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl;        bis(pentamethylcyclopentadienyl)zirconium dimethyl;        ethyltetramethylcyclopentadienyl(cyclopentadienyl)zirconium        dimethyl; indenyl(cyclopentadienyl)zirconium dimethyl;        dimethylcyclopentadienyl(cyclopentadienyl)zirconium dihydride;        trimethylcyclopentadienyl(cyclopentadienyl)zirconium dihydride;        bis(pentamethylcyclopentadienyl)zirconium dihydride;        indenyl(cyclopentadienyl)zirconium dihydride;        trimethylsilylcyclopentadienyl(cyclopentadienyl)zirconium        dimethyl;        trimethylsilylcyclopentadienyl(cyclopentadienyl)zirconium        dihydride;        trifluoromethylcyclopentadienyl(cyclopentadienyl)zirconium        dimethyl;        trifluoromethylcyclopentadienyl(cyclopentadienyl)zirconium        dimethyl;        trifluoromethylcyclopentadienyl(cyclopentadienyl)zirconium        dihydride;        bis(cyclopentadienyl)(trimethylsilyl)(methyl)zirconium;        bis(cyclopentadienyl)(triphenylsilyl)(methyl)zirconium;        bis(cyclopentadienyl)[tris(dimethylsilyl)silyl](methyl)zirconium;        bis(cyclopentadienyl)[bis(methylsilyl)silyl](methyl)zirconium;        bis(cyclopentadienyl)(trimethylsilyl)(trimethylsilyl        methyl)zirconium;        bis(cyclopentadienyl)(trimethylsilyl)(benzyl)zirconium;        methylenebis(cyclopentadienyl)zirconium dimethyl;        ethylenebis(cyclopentadienyl)zirconium dimethyl;        isopropylidenebis(cyclopentadienyl)zirconium dimethyl;        dimethylsilylbis(cyclopentadienyl)zirconium dimethyl;        methylenebis(cyclopentadienyl)zirconium dimethyl;        ethylenebis(cyclopentadienyl)zirconium dimethyl;        isopropylidenebis(cyclopentadienyl)zirconium dimethyl;        dimethylsilylbis(cyclopentadienyl)zirconium dimethyl;        methylenebis(cyclopentadienyl)zirconium dihydride;        ethylenebis(cyclopentadienyl)zirconium dihydride;        isopropylidenebis(cyclopentadienyl)zirconium dihydride;        dimethylsilylbis(cyclopentadienyl)zirconium dihydride.;        (Pentamethylcyclopentadienyl)zirconium trimethyl;        (Pentamethylcyclopentadienyl)zirconium triphenyl;        (Pentamethylcyclopentadienyl)zirconium tribenzyl;        (Pentamethylcyclopentadienyl)zirconium trimethyl;        (Cyclopentadienyl)zirconium trimethyl;        (Cyclopentadienyl)zirconium triphenyl;        (Cyclopentadienyl)zirconium tribenzyl;        (Cyclopentadienyl)zirconium trimethyl;        (ethylcyclopentadienyl)zirconium trimethyl;        (Methylcyclopentadienyl)zirconium triphenyl;        (Methylcyclopentadienyl)zirconium tribenzyl;        (Methylcyclopentadienyl)zirconium trimethyl;        (Dimethylcyclopentadienyl)zirconium trimethyl;        (Trimethylcyclopentadienyl)zirconium trimethyl;        (Trimethylsilylcyclopentadienyl)zirconium trimethyl;        (Tetramethylcyclopentadienyl)zirconium trimethyl;        Indenylzirconium trimethyl; Fluorenylzirconium trimethyl;        Bis(cyclopentadienyl)zirconium dimethyl;        Bis(cyclopentadienl)zirconium diphenyl;        Bis(cyclopentadienyl)zirconium dibenzyl;        Bis(cyclopentadienyl)zirconium dimethyl;        Bis(cyclopentadienyl)zirconium diethyl;        Bis(cyclopentadienyl)zirconium dihydride;        Bis(cyclopentadienyl)zirconium dichlorohydride;        Bis(methylcyclopentadienyl)zirconium dimethyl;        Bis(methylcyclopentadienyl)zirconium diphenyl;        Bis(methylcyclopentadienyl)zirconium dibenzyl;        Bis(methylcyclopentadienyl)zirconium dimethyl;        Bis(pentamethylcyclopentadienyl)zirconium dimethyl;        Bis(pentamethylcyclopentadienyl)zirconium dimethyl;        Bis(pentamethylcyclopentadienyl)zirconium dibenzyl;        Bis(pentamethylcyclopentadienyl)zirconium methylmethyl;        Bis(pentamethylcyclopentadienyl)zirconium methylhydride;        Ethylenebis(indenyl)zirconium dimethyl;        Ethylenebis(indenyl)zirconium dimethyl;        Ethylenebis(tetrahydroindenyl)zirconium dimethyl;        Ethylenebis(tetrahydroindenyl)zirconium dimethyl;        Dimethylsilylenebis(cyclopentadienyl)zirconium dimethyl;        Dimethylsilylenebis(cyclopentadienyl)zirconium dimethyl;        Isopropylidene(cyclopentadienyl)(9fluorenyl)zirconium dimethyl;        Phenylmethylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium        dimethyl;        Diphenylmethylene(cyclopentadienyl)(9-fluorenyl)zirconium        dimethyl; Ethylene(cyclopentadienyl)(9-fluorenyl)zirconium        dimethyl;        Cyclohyxylidene(cyclopentadienyl)(9-fluorenyl)zirconium        dimethyl;        Cyclopentylidene(cyclopentadienyl)(9-fluorenyl)zirconium        dimethyl;        Cyclobutylidene(cyclopentadienyl)(9-fluorenyl)zirconium        dimethyl;        Dimethylsilylene(cyclopentadienyl)(9-fluorenyl)zirconium        dimethyl; Dimethylsilylenebis(2,3,5-trim        ethylcyclopentadienyl)zirconium dimethyl;        Dimethylsilylenebis(2,3,5-trimethylcyclopentadienyl)zirconium        dimethyl; Dimethylsilylenebis(indenyl)zirconium dimethyl;        Zirconium tetramethyl; Zirconium tetrabenzyl; Zirconium        tetramethyl; Zirconium tetramethyl; Zirconium butoxytrimethyl;        Zirconium dibutoxydimethyl; Bis(2,5-di-t-butylphenoxy)zirconium        dimethyl; Bis(2,5-di-t-butylphenoxy)zirconium dimethyl;        Zirconium bis(acetylacetonate)dimethyl;        dimethylsilyl(tetramethylcyclopentadienyl)cycldodecyloamido)titanium        dimethyl;        dimethylsilyl(tetra-methyleyclo-pentadienyl)(1-adamantylamido)titanium        dimethyl;        dimethylsilyl(tetramethylcyclopentadienyl)(t-butylamido)titanium        dimethyl; cyclopentadienylzirconium trimethyl;        cyclopentadienylzirconium triethyl; cyclopentadienylzirconium        tripropyl; cyclopentadienyltitanium trimethyl;        cyclopentadienyltitanium triphenyl; cyclopentadienylscandium        bis(p-tolyl); cyclopentadienylchromium 2,4-pentadienyl;        (pentamethylcyclopentadienyl)yttrium        bis(bistrimethylsilylmethyl);        (pentamethylcyclopentadienyl)scandium        bis(bistrimethylsilylmethyl); pentamethylcyclopentadienyl        lanthanum bis(bistrimethyl-silylmethyl);        [1,1′-dimethylsilanylene-bis(2-methyl-indenyl)]hafnium dimethyl;        [1,1′-dimethylsilanylene-bis(2-methyl-4-phenyl-lindenyl)]hafnium        dimethyl;        [1,1′-dimethylsilanylene-bis(2-methy4-naphthyl-2-yl-lindenyl)]hafnium        dimethyl; diphenylmethylene (cyclopentadienyl)(fluorenyl)hafnium        dimethyl;        [(4-n-butylphenyl)(4-t-butylphenyl)methylene](cyclopentadienyl)(fluorenyl)hafnium        dimethyl; dimethylsilanylene        (tetramethylcyclopentadienyl)(N-adamantylamido) titanium        dimethyl; dimethylsilanylene        (tetramethylcyclopentadienyl)(N-t-butylamido)titanium dimethyl;        bis(4-[triethylsilyl])methylene (cyclopentadienyl)        (fluorenyl)hafnium dimethyl; bis(4-[triethylsilyl])methylene        (cyclopentadienyl) (2,7-di-t-butylfluorenyl)hafnium dimethyl;

The following non-metallocene olefin polymerization catalysts areactivable by invention partially fluorinated discrete activators:

bis(di-trimethylsilylamido)zirconium dibenzyl;bis(ditrimethylsilylamido)hafnium dibenzyl;bis(di-trimethylsilylamido)titanium dibenzyl;bis(di-trimethylsilylamido)zirconium dimethyl;bis(ditrimethylsilylamido)hafnium dimethyl;bis(di-trimethylsilylamido)titanium dimethyl;bis(di-isobutylamido)hafnium dimethyl; bis(di-tertbutylamido)zirconiumdimethyl; (di-cyclohexylamido)(di-trimethylsilylamido)titaniumdihydride; tris(di-trimethylsilylamido)zirconium methyl;tris(di-triphenylgermylamido)hafnium methyl;bis(di-trimethylsilylamido)zirconium dimethyl;bis(ditrimethylsilylamido)hafnium dimethyl;bis(di-trimethylsilylamido)titanium dimethyl;bis(di-phenylsilylamido)zirconium dimethyl; bis(di-trimethylsilylamido)hafnium dimethyl; bis(di-trimethylsilylamido)titanium dimethyl.

EXAMPLES

The following examples are presented to illustrate the foregoingdiscussion. All parts, proportions, and percentages are by weight unlessotherwise indicated. The examples are directed to particular inventionembodiments; they do not limit the invention in any specific respect.

Preparation of BrC₁₀H₃F₄: The preparation of BrC₁₀H₃F₄ was as describedin Journal of the Chemical Society (C)1971, pp. 604.

Synthesis of [Li(Et₂O)2.5][B(C₁₀H₃F₄)₄]: Butyl lithium in hexanes (4.2milliliters, 1.6M, Aldrich)was added to a cold (−78° C, acetone/dry icebath)diethylether solution of BrC₁₀H₃F₄ (1.870 grams). The reactionmixture was stirred for 30 minutes. Boron trichloride (1.67 milliliter,1.0M, Aldrich)was added to the reaction, after which the cold bath wasremoved. The reaction was allowed to reach room temperature. Afterwards,the ether was replaced with methylene chloride, and the product wasextracted by filtration. The solvent was removed, and the producttriturated with pentane. (yellow crystalline solid, 1.422 grams, 82%)¹⁹F NMR (CD2Cl2, 25 C): −153.8 (q, 8F), −164.5 (t, 4F), −165.8 (t, 4F).

Synthesis of [4-tBu-C₆H₄NMe₂H][B(C₁₀H₃F₄)₄]: 4-tBu-C₆H₄ NMe₂HCl (0.293grams)was added to a methylene chloride solution of[Li(Et₂O)_(2.5)][B(C₁₀H₃F₄)₄](1.422 grams). The mixture was stirred for1 hour. Lithium chloride precipitated and was collected by filtration.The filtrate was triturated and washed with pentane yielding a whitecrystalline solid. This solid was characterized by NMR spectroscopy.

Polymerization: Polymerizations using dimethylsilylbis(indenyl)hafniumdimethyl as the polymerization catalyst were carried out in a 1-literstirred reactor with continuous reactant feed and continuous productwithdrawal. The solvent was hexane. Ethylene and propylene were purifiedover alumina and molecular sieve beds. Toluene for preparing catalystsolutions was also purified using this technique. Metering pumps wereused for all feeds except for ethylene, which as a gas flowed under itsown pressure through a mass-flow controller. Reactor temperature wascontrolled in these examples by circulating water through a reactorcooling jacket. The reactors were maintained pressurized to above thereactant-mixture vapor pressure to keep the reactants liquefied. Thereactors were operated liquid-full. Residence time was set by reactorvolumes and flow rates. Residence time, defined as the average timereactants spend within the reactor was 5-50 minutes.

Ethylene and propylene feeds were combined into one stream and thenmixed with a 0° C., pre-chilled hexane stream. Polymer composition wascontrolled by the relative monomer(s)amount fed to the reactor. Enoughhexane tri-n-octyl aluminum scavenger solution was added to the combinedsolvent and monomer stream, just before the feed entered the reactor, tofurther reduce the catalyst poison concentration. Catalyst componentsmixed in toluene were separately pumped to the reactor and injectedthrough a separate port.

Product exited through a pressure control valve that reduced thepressure to atmospheric. This caused dissolved, unconverted monomer toflash into a gas, which was vented from the top of a vapor-liquidseparator. The liquid, comprising mainly polymer and solvent, flowed outof the separator bottom and was collected for the polymer solution.Invention polymers were recovered by steam stripping followed by drying,or by precipitating them with a polar solvent such as acetone, followedby residual solvent evaporation under heat and vacuum.

Polymer product was characterized by Mooney viscosity (MooneyViscometer, ASTM D-1648), ethylene content (by FTIR, ASTM D-3900), meltor glass transition temperature (by Differential Scanning Calorimetry(DSC)), and molecular weight (by Gel Permeation Chromatography (GPC)).GPC, as used to characterize invention products, has been described inseveral publications, notably U.S. Pat. No. 4,989,436. Molecular weightand composition measurements are described in G. Ver Strate, C.Cozewith, S. Ju, Macromolecules, 21, 3360 (1988). DSC was used tocharacterize invention products using a standard protocol of loading thecalorimeter at 20° C. with a specimen free of molding strains, annealingat room temperature for 40 hours, cooling the sample to −75° C.,scanning to 180° C. at 10° C./min., cooling to −75° C., and re-runningthe scan. T_(g), T_(m), and heat of fusion were evaluated. In somecases, low melting crystallinity was not seen on the second scan as itmay take many hours to develop even at low temperatures. Polymermolecular weight is controlled by reactor temperature, monomerconcentration, and by the addition of chain transfer agents such ashydrogen.

Polymer solution samples were analyzed for polymer concentration. Fromthis measurement and the reactor feed rates, polymerization rates couldbe determined using material balances. Monomer conversions were thencalculated from the rate and composition data

A polymerization series was carried out to demonstrate inventionproducts and processes. Table 1 shows reactor conditions, polymeranalyses. Table 2 shows polymerization results. TABLE 1 Productcollection Monomer Conc., Time, poly rate, % C2 in Feeds, g/hr cat feed,Res time, Catalyst^(a) Activator^(b) Wt. g % min g/hr EP ML Temp, ° C.C2═ C4═ g/hr min W I 1232 9.0 20 331.5 12.6 7.3 80 53.7 811.5 0.007479.36 W I 1253.2 6.9 20 260.2 13.4 10.8 80 53.7 811.5 0.0042 9.07 W II1508.7 14.0 20 634.6 12.8 2.8 60 75 811.5 0.014 8.29 W II 1496.1 13.3 20596.9 11.5 3.3 60 75 811.5 0.01073 8.29 W II 1447 11.3 20 488.8 12.3 5.460 75 811.5 0.00747 8.36 W II 1267.4 10.2 20 387.1 14.6 9.8 60 75 811.50.0042 9.21^(a)W is dimethylsilylbis(indenyl)hafnium dimethyl^(b)I is [4-tBu-C₆H₄N(CH₃)₂H][B(C₁₀H₃F₄)₄] II is[C₆H₅N(CH₃)₂H][B(C₆F₅)₄]

TABLE 2 Monomer Catalyst catalyst Conv., % Efficiency cat Scav/Catprecursor^(a) Activator^(b) C2═ C3═ (g/g) Kg/mole) (mol/hr) (mol/mol)C3/C6 ratio Mw, Lalls W I 77.7 35.7 44382 21969 1.51E−05 20.9 15% W I64.8 27.8 61944 30663 8.48E−06 37.3 16% W II 108.6 68.2 45326 224372.83E−05 11.2 7% 129629 W II 91.8 65.1 55633 27539 2.17E−05 14.6 8%134533 W II 80.2 52.8 65435 32391 1.51E−05 20.9 11% 153071 W II 75.540.7 82158 45619 8.48E−06 37.3 13% 176126^(a)W is dimethylsilylbis(indenyl)hafnium dimethyl^(b)I is [4-tBu-C₆H₄N(CH₃)₂H][B(C₁₀H₃F₄)₄] II is[C₆H₅N(CH₃)₂H][B(C₆F₅)₄]

While certain representative embodiments and details have been shown toillustrate the invention, it will be apparent to skilled artisans thatvarious process and product changes from those disclosed in thisapplication may be made without departing from this invention's scope,which the appended claims define.

All cited patents, test procedures, priority documents, and other citeddocuments are fully incorporated by reference to the extent that thismaterial is consistent with this specification and for all jurisdictionsin which such incorporation is permitted.

Certain features of the present invention are described in terms of aset of numerical upper limits and a set of numerical lower limits. Thisspecification discloses all ranges formed by any combination of theselimits. All combinations of these limits are within the scope of theinvention unless otherwise indicated.

1. An activator comprising an anionic or neutral central core comprisingat least one Group-13 atom connected to three or four, fused-ringassemblies comprising: a first aromatic ring that isperhydridosubstituted; and a second aromatic ring that isperfluorosubstituted.
 2. The activator of claim 1 wherein at least onefused-ring assembly is a naphthyl-based radical.
 3. The activator ofclaim 2 wherein each fused-ring assembly is a naphthyl-based radical. 4.The activator of claim 1 wherein the Group-13 atom is boron.
 5. Theactivator of claim 1 wherein the activator istris(5,6,7,8-tetrafluoro)napth-2-yl borane.
 6. The activator of claim 1comprising four fused-ring assemblies and a cation, wherein the cationis one of anilinium and ammonium cations, trityl carbenium cations,Group-11 metal cations, silylium cations, the cations of the hydratedsalts of Group-1 or -2 metals, and derivatives of the foregoinganilinium, ammonium, trityl carbenium, and silylium cations containingC₁-C₂₀ hydrocarbyl, hydrocarbylsilyl, or hydrocarbylamine substituentsfor one or more cation hydrogen atoms.
 7. The activator of claim 1wherein the central core is tetrakis(5,6,7,8-tetrafluoro) napth-2-ylborate.
 8. The activator of claim 4 wherein the first aromatic ring isdistal to the boron atom.
 9. The activator of claim 4 wherein the secondaromatic ring is distal to the boron atom.
 10. A catalyst systemcomprising at least one transition metal olefin polymerization catalystprecursor; and the activator of any of claim
 4. 11. A transition metalolefin polymerization catalyst comprising the reaction product of atleast one transition metal olefin polymerization catalyst precursor andthe activator of any of claim
 4. 12. A method for producing polymercomprising providing the catalyst of claim 11; providing monomer(s); andcombining the catalyst and the monomer under polymerization conditions.13. A method of preparing a cocatalyst activator comprising providing3-bromothiophene; providing perfluorophenyl magnesium bromide; reactingthe thiophene with the magnesium bromide; reducing the product of step(c); reacting the product of step (d) with boron trichloride; reactingthe product of step (e) with a quaternary nitrogen chloride.
 14. Anolefin polymerization process comprising: providing olefin monomer(s);providing transition metal olefin polymerization catalyst precursor(s)capable of polymerizing olefins after activation; providing theactivator(s) of claim 8; contacting the catalyst precursor(s) with theactivator(s) to form activated catalyst(s) and non-coordinatinganion(s); and contacting the activated catalyst(s) with the olefinmonomer(s)
 15. An olefin polymerization process comprising: providingolefin monomer(s); providing at least one catalyst precursor(s) capableof polymerizing olefins after activation; providing the activator(s) ofclaim 13; contacting the catalyst precursor(s) with the activator(s) toform activated catalyst(s) and non-coordinating anion(s); and contactingthe activated catalyst(s) with the olefin monomer(s).
 16. An activatorhaving the following formula:

[Ct]+ is a cation capable of abstracting a ligand from a catalystprecursor.
 17. An activator having the following formula:


18. An olefin polymerization process comprising: providing olefinmonomer(s); providing transition metal olefin polymerization catalystprecursor(s) capable of polymerizing olefins after activation; providingthe activator(s) of claim 9; contacting the catalyst precursor(s) withthe activator(s) to form activated catalyst(s) and non-coordinatinganion(s); and contacting the activated catalyst(s) with the olefinmonomer(s)
 19. An activator having the following formula:

[Ct]+ is a cation capable of abstracting a ligand from a catalystprecursor.
 20. An activator having the following formula: